Cyan color formers for color photography

ABSTRACT

WHEREIN R1 is H or alkyl; R2 is H, halogen or SO3X, X being H or a water-solubilizing cation; A is an electron-releasing group; Y is -O- or -CH2-; R6 is H or carboxyphenylene; R7 is an alkyl group of one to 18 carbon atoms, and n is an integer from one to three.   Light-sensitive silver halide photographic emulsions containing a nondiffusing cyan coupler having one of the following formulas:

United States Patent [72] Inventors Alex P. Altavllla Johnson City; Walter Hoffstadt, Vestal; Emil Rauch, Port Dickinson, all of N.Y. 21 1 Appl. No. 749,650 [22] Filed Aug. 2, I968 [45] Patented Nov. 23, 1971 [73] Assignee GAF Corporation New York, N .Y.

[54] CYAN COLOR FORMERS FOR COLOR PHOTOGRAPHY 16 Claims, 1 Drawing Fig. [52] U.S. Cl 96/100, 96/9 [51] lnt.Cl G03c 1/40 [50] Field of Search 96/50, 100, 9

[56] References Cited UNITED STATES PATENTS 3,226,230 12/1965 Van Poucke et al 96/100 X 3,244,520 4/1966 Schulte et a1. 96/100 X 3,488,193 1/1970 Eynde et a1. 96/100 X FOREIGN PATENTS 902,266 8/1962 England 96/100 Primary Examiner-Norman G. Torchin Assistant Examiner-John L. Goodrow Attorneys-Walter G. Hensel, Samson B. Leavitt and Walter C. Kehm ABSTRACT: Light-sensitive silver halide photographic emulsions containing a nondiffusing cyan coupler having one of the following formulas:

OH p. -f

CON-Q R1 A 000x R7 OH I a Y(CHz),.-C 0. N CO'N- wherein R is H or alkyl; R is H, halogen or SO X, X being H or a water-solubilizing cation; A is an electron-releasing group; Y is -O- or -CH,; R is H or carboxyphenylene; R is an alkyl group of one to 18 carbon atoms, and n is an integer from one to three.

DENSITY PATENTEDNUV 23 I971 3,622,337

l I I u 600 I O0 750 WAVELENGTH IN MILLIMICRONS l/"/ V/aN'l IRS ABSORPTION CURVES OF DYES ALEX PALTAVILLA FORMED AFTER REVERSAL WALTER HOFFSTADT ATTORNEYS 1 CYAN coLoii runners r61: coLok PHOTOGRAPHY The production of colored photographic images according to techniques based upon the reaction of color-forming or coloncoupling components with the oxidation products of a primary aromatic amino developing agent is, of course, wellestablished practice being extensively described in the published literature both patent and otherwise. In processes of this type, the subtractive method of color reproduction is ordinarily employed, i.e., the point-to-point color composition is a function of the combined absorption spectra of the subtractive primary color component images present thereat, i.e., cyan, magenta and yellow disposed in registered superposition. in general, the multilayer color systems in use today employ couplers of the pyrazolone type for producing the magenta dye image; reactive ketomethylene compounds for producing the yellow dye images and phenol or naphthol-type couplers for producing the cyan image. Color development effected with the aforedescribed coupling materials results in the imagewise formation of dyestufi in situ with the silver images, the latter being subsequently bleached or otherwise removed to yield pure dye images.

One of the major difficulties confronting the practioners of color photography relates to the provision of color coupler materials capable of yielding, upon photographic coupling development, dyestuffs having the requisite spectral absorption characteristics, i.e., purity of color. As is well known, each of the yellow, magenta and cyan dye images functions to modulate white light in accordance with its spectral absorption characteristics. Ideally, the yellow, magenta and cyan dye images should exhibit maximum absorption density in the blue, green and red spectral regions respectively. Any significant departure from such spectral behavior presents manifoldproblems as regards the achievement of a quality color reproduction. However, in actual practice this ideal condition is approached but never achieved. The color couplers currently enjoying extensive commercial use are uniformly characterized in that their dyestuff products exhibit an undesirable degree of spurious spectral absorption. The consequences as regards the effects upon accuracy of color reproduction are self-evident. For example, to the extent that the fugitive spectral absorption of a given subtractive color primary is coterminous with that of a second primary, it contributes to the absorption of said second primary with the inevitable consequence that the overall color balance of the reproduction obtained will exhibit an undesired color shift in favor of said second subtractive primary. Thus, to the extent that magenta which, ideally, is completely absorptive for green radiation, absorbs in the red, its spectral characteristics are common to that of the cyan color componentJ For purposes of establishing net color rendition, the magenta dyestuff must be regarded as containing a cyan component.

Departures from the desired absorption spectra have been found to be particularly manifest in connection with the cyan color formers. An additional source of difficulty further detracting from the suitability of the cyan couplers thus far provided stems from the instability characterizing their dyestuff products, such a condition being noted to obtain under even moderately severe conditions of heat, humidity, light exposure, etc. The results of continued observation establish that the cyan dyestuff produced undergoes decomposition under such conditions being thus converted to a brownish-colored product. The deleterious effects of light, heat, humidity, etc. impose, of course, rather stringent limitations upon the range of cyan coupler selection.

In an effort to overcome or otherwise alleviate the foregoing and related disadvantages, considerable industrial effort has centered around the research ami development of cyan coupling materials capable of yielding dyestuffs possessed of the requisite stability to the effects of heat, humidity and light,

as well as the desired spectral absorption characteristics. As a consequence, certain classes of cyan couplers have been evolved which for the most part, have satisfied at least the minimum requirements of the art. Typical representatives of such coupler materials include those of the following structural formulas;

OH ()0 0H e Alkyl 0 OH m w 0H SOHH NAlkyl Alkyl The above couplers have enjoyed a considerable measure of commercial acceptance since the dyestuff images produced therewith exhibit an acceptable level of stability to light, humidity, etc. However, the results are far from optimum as regards the spectral absorption characteristics of such dyestuffs. Thus, dyestuffs formed from A have suitably low absorption in blue, but the red absorption should be farther out (A,,,=655). The hue is bluer than desired, and the stability is poor. In the case of dyestuffs formed from B, the blue absorption is higher than with A, and the red absorption should be shorter 705 the hue being green. The stability is satisfactory.

In view of the advantageous stability properties possessed .by cyan coupler materials having the approximate molecular resulted from efiorts to provide modifications of such materials, e.g., position isomers, substituted derivatives and the like,

in order to retain their advantageous stability properties but at the same time realizing more favorable absorption spectra.

Much of the effort has involved a rather detailed evaluation of the individual effects exerted by each of the substituent groups, e.g., dialkylamino and solubilizing groups, upon the overall properties of the parent coupler molecule. In this connection it has been ascertained, for example, that the relative positioning of the solubilizing substituent, e.g., sulfo, carboxyl, has a pronounced influence upon both the absorption spectra and stability of the dyestuff. Thus, we have found that if couplers of the type illustrated in formula B above be modified to the extent that the solubilizing group in the 5-position of the anilido group is separated from the phenyl ring by insertion of certain alkyl, aryl or ether groups, the coupler will yields a dye having a desirable shift in peak absorption to the shorter wavelength range. Moreover, the dyestufi' images obtained display an exceptional resistance to the deleterious effects of humidity, light, etc.

Thus, a primary object of the present invention resides in the provision of cyan coupler compounds capable of yielding, on color-coupling development, dyestuff images wherein the aforedescribed difficulties regarding spectral absorption, stability, etc. are eliminated or at least mitigated to a substantial degree.

A further object of the present invention resides in the provision of cyan coupler materials which produce dye images having low blue light absorption and high red light absorption.

A further object of the present invention resides in the provision of cyan coupler materials which yield dyestuffs having an exceptional degree of stability to the effects of heat, light and humidity.

Yet another object of the present invention resides in the provision of light-sensitive silver halide emulsions containing such coupling materials. V g j Other objects of the present invention will become apparent hereinafter as the description proceeds.

The foregoing and related objects are accomplished in accordance with the present invention by the use of cyancoupling compounds of the following general formula:

wherein R represents hydrogen or alkyl of from one to 18 carbon atoms; R represents halogen, hydrogen or SO X wherein X represents hydrogen or a water solubilizing cation, e. g. sodium, potassium, ammonium, substituted ammonium and the like; A represents an electron-releasing group, especially a mildly electropositive substituent, preferably substituted ortho or para to the CON(R, group, e.g. alkyl of from six to 18 carbon atoms, of from six to 18 carbon atoms,

wherein R represents lower alkyl of from one to four carbon atoms, e.g. methyl, ethyl, etc. and R represents alkyl of from eight to 18 carbon atoms; Y represents S, --O or (CH m being an integer from 1 to 4, and B represents a group selected from (a) alkylsulfonic and arylsulfonic acid groups and their salts, especially their sodium, potassium, ammonium and substituted ammonium salts, (b)

co OX wherein R represents hydrogen or carboxyphenylene, e. g.

R represents alkyl of one to 18 carbon atoms, n is an integer from i to 3 and has the aforedefined significance.

Cyan couplers encompassed by the above formula are of exceptional value in color photographic applications since they produce cyan dyestuffs having low green and blue and high red absorption characteristics as well as excellent stability upon exposure to heat and light. Moreover, such couplers possess exceptional reactivity with oxidized developing agents thus providing high-speed color reproduction.

.3 iltb nq z st sir h Peak e ser h repss OR wherein R represents alkyl dyestuffs are separated by about 30 millimicrons, resulting in a considerable and desirable reduction in green absorption.

Without intending to be bound by any theory it has been postulated that the introduction of a substituent which releases electrons such as alkoxy, dialkylamino, thioalkyl, i.e., a substituent which is mildly electropositive, into the ortho'- position of the naphthamide molecule shifts the spectral absorption towards the shorter wave lengths resulting in the obtention of a truer cyan.

Similar results are observed, albeit to a somewhat lesser extent, with the substitution of such electron-releasing substituents in the para'-position. Usually, such substituents will be provided with a nondiffusing group such as long chain alkyl, which in turn, requires the introduction of an additional solubilizing group in order to impart the requisite hydrophilic character to the coupler molecule. conventionally, this is accomplished by the use of such substituents as sulfo, carboxy and the like. However, the electron withdrawing properties of such groups are extremely powerful to the extent that undesirable shifts in the spectral absorption of the dyestuff products result. This is true despite the mildly electropositive behavior of the electron-releasing substituent. These undesired electrostatic efiects are overcome in accordance with the present invention by isolating the solubilizing functional group, e.g., carboxyl from the coupler molecule in the manner illustrated in formula C above.

in addition to the improved spectral absorption, stability, minimization of silver occlusion, etc., coupling compounds so constituted have little effect upon viscosity when incorporated into an emulsion or blend and thus less dilution is necessary to obtain the optimum coating viscosity. Furthermore, the dye images obtained therewith are formed of discrete dye particles, in contradistinction to the mush and ill-defined dye images yielded by the vast majority of the known prior art cyan couplers.

As particular examples of cyan couplers found to be eminently suitable for use in the present invention, there may be mentioned the following:

2'-(N-methyl-N-tetradecyl)-amino-5(-B-carbozyethyl 1)-1-hydro zy-2- naphthanllldeA-sulfonic acid 1'31 OH (IJHzCHC O OH l III-43141120 l CH Br CHzCHzC O OH C OOH CONH OOH uHzn 4-l;HN-(3 fi-dlearbox henyD-N-octadec l-carbamol ro lox -1- hydroxy-2 naphthanl l i e y ylp py y} A o ONE-Q 0 0 OH K o 0mg ON- 2lN-(3,5-dlcarboxyphenyl)-N-octadecylcarbamoyl-methoxy]l-hydroxy- 2-naphthanilide 0H COOH CONH-QOCHQC 0N- nHa1 OOH

4-[N-(3,5-dlcarboxyphenyl)-N-octadecylcarbamoylmethoxyl-l-hydroxy- 2-naphthanillde 0 CuHzo 2-tetradecyloxy-5-carboxymethoxy-l-hydroxy-Zmaphthanillde 2'-pentadeeyl-G'-(beta-carboxyethyl)-1-hydroxy-2-naphthanlllde C O OH CO OH Cn n The following exampies are illtistrative ofthe preparation of couplers described herein; however, such examples are not to be taken as limiting or in any way construing the present invention:

EXAMPLE 1 Preparation of 2-(N-methyl-N-tetradecyl)-amino-5'-(fi-carboxyethyl l -hydroxy-2-naphthanilide A solution is prepared comprising: 6 g. Z-(N-methyl-N-tetradecyl)-amino-5'-(,B-carboxyethylene)-l-hydroxy-2-naphthanilide which has the following structural formula:

OH CH=CHCOOII 0 ONE-- 0.2 g. PtOz 1209c. absolute methanol The above solution was placed in a Parr flask and hydrogenated under 50 p.s.i. until the required amount of hydrogen was taken up. The solution was allowed to cool to room temperature, filtered and then chilled. The solid was collected and washed with cold methanol.

Yield of coupler: 3 g.

M.P.: 78-80 C.

Analysis Calculated Found c 74.96 74.99 H 8.63 an N 5.00 5.00

(a) The 2-(N-methyl-N-tetradecyl)-amino-5-(B-carboxyethylene)-l-hydroxy-2-naphthanilide utilized in the above example was prepared according to the following procedure:

A solution comprising 14.7 g. (0.061 moles)-of 3-nitro-4- chlorocinnamic acid, 14.7 g. (0.061 moles) of N-tetradecyl-N- methylamine, 7.02 g. (0.06! moles) of triethylamine and 75 cc. dry xylene was charged into a 250 cc. one-neck flask topped with a condenser and drying tube. The reaction mixture was then heated at reflux for a period of 6 hours. The solvent was removed under aspirator vacuum followed by high vacuum. The oil obtained turned solid upon cooling, the solid was then triturated with 75 cc. of methanol and filtered. The filter cake was then recrystallized from high boiling petroleum ether (b.p.: l00 C.).

Yield of 4-(N-methyl-N-tetradecyl)-amino-3-nitro-cinnamic acid: 15 g. M.P.: l06l07 C. Color: Yellow Analysis Calculated Found (b) Preparation of 3-amino-4-(N-methyl-N-tetradecyl)- amino-cinnamic acid:

A first solution is prepared comprising:

2,600 cc. H 0

g. NaOH A second solution is prepared comprising:

800 cc. ethanol 100 g. of the product from (a) 80 cc. 6N NaOH The above solutions were heated to 65 C. The second solution was added to the first solution while stirring. When the addition was completed the reaction mixture was acidified with acetic acid at 55 C. and allowed to cool slowly to room temperature. The solid obtained was filtered and washed with Analysis Calculated Found C 74.18 74.26 H 10.37 10.00 N 7.22 7.35

(c) Preparation of 2'-(N-methyl-N-tetradecyl)-amir1o=5-(5- carboxyethylene)-l-hydroxy-Z-naphthanilide.

A solution comprising 11.6 g. (0.03 moles) of the product obtained in (b) and 7.9 g. (0.03 moles) of salol" (phenylsalicylate) were placed in a flask and heated in a metal bath at 150-155 C. under vacuum. Heating was continued until a theoretical amount of phenol distilled (l hours). The residue was then dissolved in 75 cc. of hot glacial acetic acid, charcoaled and filtered. The filtrate while still hot was diluted with 75 cc. of ethanol. The solid was collected after chilling and twice recrystallized from ethanol.

Yield: 2'-(N-methyl-N-tetradecyl)-amino-5-(B-carboxyethylene)- l -hydroxy-2-napthanilide: 12 g.

Color: Light Yellow Analysis Calculated Found C 75.24 75.58 H 8.3 8.32 N 5.02 5.16

EXAMPLE 2 Preparation of 2'-(N-methyl-N-tetradecyl)-amino-5'-(bearboxyethyl)- l -hydroxy-2-naphthanilide-4-sulfonic acid A solution is prepared comprising:

800 cc. sulfuric acid (conc.)

160 g. of the coupler obtained in example l The sulfuric acid was charged into a flask equipped with a stirrer, thermometer and drying tube. The coupler of example 1 was added in such a manner as to maintain a temperature of 38-40 C. After the addition was completed, stirring was continued for 2 hours at room temperature and the solution poured into a mixture of ice and water. The solid was filtered and washed free of sulfuric acid with water. The dried filter cake was boiled out in one liter of acetonitrile and filtered hot.

Yield: 126 g.

M.P.:2l5-2l6C. Color: White Analysis Calculated Found c 65.81 65.44 H 7.26 7.26 N 4.37 4.36 s 4.99 4.99

EXAMPLE3 Preparation of 2'-(N-methyl-N-tetradecyl)-amino-5'-(,B-

bromo-B-carboxyethyU- l -hydroxy-4-bromo-2-naphthanilide A solution is prepared comprising:

1.28 g. (0.008 m.) bromine 50.0 cc. glacial acetic acid 4.0 g. (0.007 mole) of the coupler obtained in example l A flask fitted with a stirrer and thermometer was charged with the coupler of example 2 and ml. glacial acetic acid. The bromine, dissolved in 25 ml. glacial acetic acid, was added dropwise at room temperature. Stirring was continued for 2 hours at room temperature and for 10 minutes on the steam bath. Stirring was again maintained at room temperature until solids started to precipitate. The solid was filtered off, washed with water and acetonitrile. After recrystallization from acetic acid, 2.5 g. of a white solid, melting at l82-l 83 C., was obtained.

Analysis Calculated Found C 58.49 58.48 H 6.45 6.53 N 3.39 3.86 Br 22.23 22.15

EXAMPLE 4 Preparation of 3 B-carboxyethyl )-4 N-methyl-N tetradecyl ]-amino- 1 -hydroxy-2-naphthanilide A solution is prepared comprising:

5 g. 2(-N-methyl-N-tetradecyl)-amino-5-nitrocinnamic acid cc. absolute ethyl alcohol 3 cc. cone. sulfuric acid The above reactants were charged into a flask fitted with a reflux condenser and heated at reflux for a period of 4 hours. The reaction mixture was poured into cold water and extracted with two 50 cc. portions of ether. The ether extracts were dried with magnesium sulfate, filtered and the solvent removed. The residue was used directly for the preparation of the amine. The residue was dissolved in 50 ml. ethanol. Adams catalyst was added and the hydrogenation started under 50 p.s.i.

After the calculated uptake the catalyst was filtered off and the solvent removed under vacuum. Phenyl-l-hydroxy-2- naphthoate (3.0 g.) was added to the residue and the mixture was held at ll65 C. for 5 hours and cooled to room temperature. A mixture of 32 ml. ethanol, 6 ml. water, and 3.0 g. sodium hydroxide was added at R.T. and refluxed again for 2.5 hours. Pouring into ice water containing hydrochloric acid yielded a gum which was washed with water several times. After drying, the gum was treturated with petroleum ether (l00 C. yield: 0.7 g.; M.P. 94-96 C.

Analysis Calculated Found C 74.96 74.75 H 8.63 8.38 N 5.00 4.82

The Z-(N-methyl-N-tetradecyl)-amino-5-nitrocinnamic acid utilized in the above example was prepared according to the following procedure.

A solution is prepared comprising:

3.0 g. (0.01 m.) 2-chloro-5-nitro cinnamic acid 3.0 g. (0.01 m.) N-methyl-N-tetradecyl amine 1.0 ml. triethylamine 25.0 ml. dimethylsulfoxide The above reactants were charged into a flask equipped with a stirrer and reflux condenser. The reactants were heated at reflux for a period of 5 hours. The reaction mixture was poured into ice water. The water was decanted from the oily product and the oil washed several times with fresh water. Recrystallization from methanol yielded 2.1 g. of a yellow solid. M.P. 84-85 C.

Analysis Calculated Found C 68.83 68.63 H 9. l 5 8.93 N 6.69 6.97

EXAMPLE 5 Preparation of 2'-tetradecyloxy-5'-[B-carboxy-B-(p-carboxyphenyl)-ethyl]- l-hydroxy-Z-naphthanilide Approximately 0.8 g. of 2'-tetradecoxy-5-[B-carboxy-B-(pcarboxyphenyl )-ethylene l -hydroxy2-naphthanilide was dis-' Analysis Calculated Found C 73.74 73.80 H 7.39 7.24 N 2.10 2. [8

The l-hydroxy-2-naphthanilide intermediate utilized in the above example was prepared according to the following procedure.

(a) Preparation of a-(p-carboxyphenyl)-B-(4-hydroxy-3- nitrophenyl)-acrylic acid:

A solution is prepared comprising:

38 g. (0.21 moles) Homoterephthalic acid 38.4 g. (0.23 moles) 3-nitro-4-hydroxybenzaldehyde 40 ml. Pyridine 40 ml. Acetic anhydride The above reactants were charged into a flask fitted with a stirrer and thermometer and heated for l hour at l50-l55 C. Pouring the reaction mixture into ice and hydrochloric acid yielded a gum which was washed several times with water. The gum was dissolved in dilute ammonium hydroxide and repredipated by the addition of hydrochloric acid. The solid was collected and washed with water. The filter cake was dispersed in 500 ml. glacial acetic acid and the insoluble material filtered. The filtrate was diluted with 1.000 ml. acetonitrile and chilled.

Yield: 32.3 g.

M.P.: 243-246 C.

(b) Preparation of a-(p-carboxyphenyl)-B-(3-nitro-4- tetradecoxyphenyl)-acrylic acid: a solution is prepared comprising:

9.87 g. (0.03 moles) of the product obtained from (a) 4.86 g. (0.09 moles) NaOCH 8.97 g. (0.03 moles) tetradecyl bromide 100.0 cc. absolute ethanol 100.0 cc. dimethylsulfoxide The sodium salt of the acrylic acid derivative was formed in the alcohol by the addition of NaOCl-l The isolated salt was dissolved in DMSO and heated to 95 C. Tetradecylbromide was added; stirring at 95 C. was continued for 24 hours. The reaction mixture was poured into 2]. ice water and the solid collected.

Analysis Calculated I Found c 68.55 68.57 H 7.4x 7.44 N 2.66 3.33

(c) Preparation of a-( p-Carboxyphenyl )-B-( 3-amino-4- tetradecoxyphenyl)-acrylic acid: the following solutions were prepared:

1 l g. nitro acid) Solutionl 150 cc. H 150 cc. H O) Solution ll 33 g. Na S- O 5 g. NaOH The two solutions were heated to 60 C. Solution l was added to solution ll in small portions. After the addition heating was continued for 0.5 hours. The reaction mixture was chilled and acidified. The solids were collected and recrystallized from 80 cc. glacial acetic acid.

Yield: 1.5 g. M.P.: l30l32C.

Analysis Yield: 0.8 g. M.P.: 230"23lC. Theory: C 73.74 Found: C 73.80

N 2. IO N EXAMPLE 6 Preparation of 4-carboxymethoxyl -hydroxy-2'pentadecyl-2- naphthanilide A solution is prepared comprising: 23.0 g. (0.04 m.) 4-ethoxycarbonylmethoxy- 1 -hydroxy- 2pentodecyl-Z-naphthanilide l2.0 g. NaOH 135.0 cc. Ethanol 30.0 cc. water A solution of the ester in I00 ml. ethanol was heated to boiling and treated with a mixture of 12 g. of sodium hydroxide in 30 ml. of water and 35 ml. of ethanol. The mixture was heated to boiling, cooled and diluted with water. The water solution 0 was washed with ether, acidified and extracted with ether. The

ether solution was dried and evaporated to dryness. The residue was taken up in petroleum ether (b.p. 3060 C.). After chilling the solid was collected.

Yield: 19.0 g.

Analysis Calculated Found C 74.55 74.52 H 8.28 8.15 N 2.56 2.58

The l-hydroxy2-naphthanilide intermediate utilized in the above example is prepared according to the following procedure.

(a) Preparation of ethyl-4-nitro-3-pentadecylphenoxyacetate:

A solution is prepared comprising:

0.46 g. (0.02 m.) sodium metal 7.0 g. (0.02 m.) 3-pentadecyl-4-nitro-phenol 3.0 g. (0.025 m.) ethyl-chloroacetate 10.0 ml. dimethyl formamide 20.0 ml. absolute alcohol To a solution of sodium metal (0.46 g.) in ethanol was added 3pentadecyl-4-nitrophenol (7.0 g.). After stirring briefly the ethyl chloroacetate (3.0 g.) in dimethyl formamide (10 ml.) was added. The reaction mixture was refluxed for 2 hours, cooled and diluted with water. The product was extracted with ether and the ethereal solution dried. The residue, after removal of the solvent, was taken up in methanol and chilled.

A solution is prepared comprising:

32 g. (0.0736 moles) intermediate from (a) 200 ml. absolute alcohol 200 mg. Platinum oxide The above reactants were placed in a Parr unit at 50 psi. and heated to 40 C. The reaction mixture was filtered after the required amount of hydrogen was taken up. The ethanol was removed under reduced pressure to leave a residue which solidified. It was used directly in the next reaction.

Yield: 29.8 g.

M.P.: 43-45 C. (c) Preparation of 4'-ethoxycarbonylmethoxyl -hydroxy-2'- pentadecyl-Z-naphthanilide: A solution is prepared comprismg:

29.8 g. (0.07 m.) intermediate from (b) 2l.l g. (0.08 m.) salol The above reactants were heated under vacuum for 3 hours l l at l70-l 80 C. The residue recrystallized from Cl'l Ofl,

Yield: 34.0 g. M.P.: 6l62 C.

Analysis Calculated Found C 75.09 75.09 H 8.58 8.34 N 2.43 2.46

EXAMPLE 7 Preparation of 4-{3-[N-(3,5-dicarboxyphenyl)-NoctadecylcarbamoyHpropyloxyll -hydroxy-2-naphthanilide A solution is prepared comprising:

25.0 g. (0.03 m.) of l-hydroxy-4-{ 3-[N-(3,5-dimethoxycarbonylphenyl )-N-octadecyl-carbamoyl ]propyloxy }-2- naphthanilide 135.0 ml. ethanol 12.5 g. NaOH 30.0 ml. water The solution of the ester in 100 ml. ethanol was heated to boiling and treated with a mixture of 12.5 g. NaOH in 30 ml. H and 35 ml. ethanol. The mixture was briefly refluxed andcooled. After the addition of water the solids were filtered off. The filtrate was acidified and the solid collected. This was recrystallized first from glacial acetic acid and then from ethanol. Yield: 9.3 g. m.p. l98-200C.

Analysis Calculated Found C 72.3 72.10 H 7.69 7.46 N 3.59 3.59

The 1-hydroxy-2-naphthanilide intermediate utilized in the above example was prepared according to the following procedure:

(a) Preparation of methyl-p-nitrophenoxybutyrate A solution is prepared comprising:

69.5 g. (0.5 moles) p-nitro phenol 11.5 g. (0.5 moles) sodium metal 300.0 ml. absolute alcohol 150.0 ml. DMF

68.3 g. (0.5 moles) methyl-4-chlorobutyrate Paranitrophenol was added to a solution of sodium metal in 300 ml. of absolute alcohol. The mixture was stirred and. heated under reflux for several minutes and was then diluted? with 150 ml. of dimethyl formamide. Methyl-4-chlorobutyratel was added together with a pinch of sodium iodide. The reac-E tion mixture was stirred under reflux for 36 hours. It was diluted with water and extracted with ether. After washing and drying the ether solution, the ether was removed. The residue was distilled.

Yield: 73.5 g.

B.P.: l43|53 C./0.3 mm.

Anulyslu Calculated Found C 55.23 56.70 H 5.48 5.55 N 5.86 5.64

(b) Preparation of --nitrophenoxybutyric acid:

A solution is prepared comprising:

73.5 g. of the ester obtained from (a) 40.0 g. NaOH 100.0 ml. ethanol 400.0 ml. H 0

The above reactants were charged into a flask and heated at reflux for l hour. The solution was diluted with water, acidified, and extracted with ether. After washing and drying, the ethanol solution was evaporated to dryness. This residue was extracted with 1.0 N sodium hydroxide. The sodium hydroxide solution was then acidified to give a white solid. It was recrystallized first from methanol-water apd a second time from benzene.

Yield: 20 g.

m.p.: l26-l27.5 C. (c) Preparation of -nitrophenoxybutyryl chloride:

A solution is prepared comprising:

19.5 g. (0.086 m.) butyric acid from (b) 24.0 g. (-02 m.) thionyl chloride The acid and the thionyl chloride were charged into a flask and heated at reflux for a period of 3 hours. The excess thionyl chloride was then removed under reduced pressure. The residue was used directly in the next reaction. (d) Preparation of 3',5'-Bis(methoxyearbonyl)-4-pnitrophenoxy-N-octadecylbutyranilide:

A solution is prepared comprising:

19.5 g. (0.086 in.) acid chloride obtained from (c) 39.6 g. (0.086 m.) dimethyl-5-octadecylamino-isophthalate 400.0 ml. dry pyridine The amine and acid chloride were charged into a flask and heated for 15 minutes on a steam bath. The mixture was taken up in 400 ml. pyridine and allowed to stand at R.T. for 15 hours. The mixture was filtered and the mother liquor diluted to 3 liters with water containing 12 g. of sodium hydroxine. The ppt. was dissolved in benzene and the benzene solution was dried and concentrated. The residue was dissolved in 300 ml. of warm petroleum ether (b.p. 90-l00 C.) and chilled.

Yield: 50 g. M.P.: 69-72 c.

Analysis Calculated Found C 68.23 63.49 H 8.44 8.49 N 4.) 414 (e) Preparation of 4-p-Aminophenoxy-3,5'-bis( methoxycarbonyl)-N-octadecylbutyranilide A solution is prepared comprising:

39.7 g. nitro compound from (C1) 0.2 g. PtO

200.0 ml. ethanol The above reagents were placed in a Parr hydrogenator and reduced at 45 C. and 50 psi. After the calculated uptake the catalyst was filtered out and the solvent removed under reduced pressure. The residue was used directly for the next step. (f) Preparation of l-Hydroxy-4'-{ 3-[-(3,5-dimethoxycarbonylphenyl)-N-octadecylarbamoyl]propyloxy-2-naphthanilide A solution is prepared comprising:

38.0 g. (0.059 m.) amine from (c) 16.4 g. (0.062 m.) salol The above reactants were charged into a flask and heated at l70-l C. under reduced pressure for 3 hours. The residue was stirred at room temperature with methanol until it solidified. This solid was then treated with methanol again in a Waring Blender. It was recrystallized first from acetic acid and finally from acetonitrile.

Yield: 25 g.

M.P.: 103-106 C.

EXAMPLE 8 Preparation of 2[N-(3,5-dicarboxyphenyl)-N-octadecylcarbamoylmethoxy] 1-hydroxy-2-naphthanilide A solution is prepared comprising: 5.0 g. of 2-[N-(3,5-bismethoxycarbonylphenyl)-N-octadecylcarbamoylmethoxy]- l -hydroxy-2-naphthanilide 2.5 g. NaOH 27.0 ml. ethanol 51 .wa st The preceding reactants were charged into a Ilask and heated to boiling. The reaction solution was chilled immediately, diluted with water, and acidified with 6N HCl. The solid was filtered and recrystallized from glacial acetic acid.

Yield: 1 g. M.P.: l84-l87 C.

Analysis Calculated Found C 7 l .8 72.02 H 7.45 7.14 N 3 .72 3.67

water, and recrystallized from methanol.

Yield: 21 g. M.P.: 57-58 C.

Analysis Calculated Found c 67.45 67.49 H 8.13 8.27 N 4.38 4.26

A solution is prepared comprising:

19.0 g. (0.029 m.) nitro compound from (a) 0.2 g. PtO

100.0 ml. ethanol The above reactants were placed in a Parr shaker and hydrogenated under 50 p.s.i. at room temperature until the required amount of hydrogen was taken up. The catalyst was filtered out and the filtrate chilled.

Yield: 1 6 g. M.P.: 57-58 C.

Analysis Calculated Found C 70.8 71.05 H 8.85 8.85

(d) Preparation of 2'-[N-(3,5-bismethoxycarbonylphenyl)-N- octadecylcarbamoylmethoxyl l-hydroxy-2-naphthanilide A solution is prepared comprising:

39.0 g. (0.064 m.) amino derivative from (b) 16.9 g. (0.064 m.) salol The preceding reactants were charged into a flask and heated at 170180 C. under reduced pressure for 1.5 hours. The residue was stirred with methanol until solid and recrystallized from glacial acetic acid.

Yield: 34 g.

M.P.: 1l2-114C.

Analysis Calculated Found C 72.3 72.49 H 7.70 7.40

EXAMPLE 9 Preparation of 4'-[N-(3,S-dicarboxyphenyl)-N-octadecylcarbamoylmethoxyll -hydroxy-2-naphthanilide The series of reactions employed inthe synthesis of the above coupler material was identical with that described in example 8 except that the o-nitrophenoxy acetyl chloride employed as the starting material was replaced by the same amount of the paraisomer.

The coupler product obtained had a melting point of Analysis Calculated Found C 71 .8 72.0 H 7.41 7.33 N 3.72 3.48

EXAMPLE 10 Preparation of l-hydroxy-2-[ 2-tetradecyloxy-5 -(B-carboxyethyl)]-naphthanilide A solution is prepared comprising:

2.6 g. (0.007 m.) of /3-(3-amino-4-tetradecyloxyphenyl)propionic acid 1.8 g. (0.007 m.) salol 4.0 ml. ethanol 1.0 ml. triethylamine The above mixture was heated on a steam bath to dissolve and drive off excess solvents. The residue was heated in a metal bath at C. for 2 hours. After cooling, the reaction mixture was triturated with methanol containing a small amount of acetic acid. After chilling, the solids were collected by filtration and recrystallized from ethanol.

Yield: 2.1 g.

M.P.: 107-109 C.

The propionic acid intermediate utilized in the above example was prepared according to the following procedure. (a) Preparation of B-(3-Acetylamino-4-hydroxyphenyl)propionic acid 5.7 of 3-acetylamino-4-hydroxycinnamic acid in 75 ml. ethanol was converted to the sodium salt by the addition of 6N NaOH. The resulting solution was hydrogenated using palladium on charcoal at room temperature and 50 lbs. pressure.

After the theoretical uptake the catalyst was filtered out and the filtrate acidified. The resulting salts were filtered off and the filtrate evaporated to dryness. The residue was recrystallized from 75 ml. water.

Yield: 5.1 g.

Analysis Calculated Found C 59.41 59.64 H 5 .86 5.72 N 6.28 6.43

(b) Preparation of ,8-(3-Acetylamino-4-tetradecyloxyphenyl)propionic acid A solution is prepared comprising: 5.0 g. (0.022 m.) propionic acid from (a) 2.4 g. (0.044 m.) sodium methoxide 1 1.1 g. (0.04 m.) tetradecyl bromide 50.0 ml. absolute alcohol The above reagents were charged into a 100 ml. flask and refluxed for 7 hours with stirring. After the salts were filtered off, the filtrate was chilled. The product was filtered off and washed with 25 ml. cold ethanol. The filter cake was recrystallized from acetonitrile-glacial acetic acid (9:1

Yield: 7.1 g. M.P.: 108110C.

Analysis Found 3.52; 3.46

Calculated N 3.34

(c) Preparation of yl)propionic acid A solution is prepared comprising:

6.5 g. propionic acid from (b) 35.0 ml. ethanol 70.0 ml. 6N sodium hydroxide The above reagents were refluxed for 4 hours and poured into 400 ml. water. The solution was acidified with 6N hydrochloric acid and chilled. The solids was collected, washed with water and recrystallized from 100 ml. acetonitrile and 25 ml. acetic acid.

Yield: 4.2 g.

M.P.: -192 C.

B-( 3-Amino-4-tetradecyloxyphen- Calculated N 3.71

The color couplers contemplated by the present invention can be incorporated in a photographic light sensitive silver hawe have ascertained that aqueous or alcoholic solutions of organic bases including ammonium hydroxide, alkali metals are especially suitable for this purpose. The choice of alkali to effect solution of the coupler is unimportant since it is the coupler structure per se which accounts for the highly desirable photographic properties previously enunciated. lt is, of course, manifest that no alkaline solubilizing medium should be chosen which would be damaging or deleterious to the photographic emulsion in which the coupler is to be incorporated.

The color-forming components contemplated herein can also be incorporated in a gelatino silver halide photographic emulsion by the dispersion method. The water immiscible high boiling oily solvents commonly used in preparing coupler dispersions include high boiling esters, alcohols, ketones, or mixtures thereof. The chemical literature and patents contain such listings of these solvents and it is not considered necessary to reproduce such information in the present specification.

Suitable developing agents include the various alkyl phenylenediamines as exemplified by the following: 4- aminoaniline, 4-ethylaminoaniline, 2-diethylaminoaniline, 4- dialkylaminoaniline, e.g., 4-dimethylaminoaniline, 4- diethylaminoaniline, 4-[N-(,B-hydroxyethyl)-N-ethyl] aminoaniline, 4amino-N-ethyl-N-(B-methanesulfonamidoethyl)-2-methylaniline sulfate and the like. The above developing agents are preferably used in the form of their salts such as the hydrochloride or hydrosulfate as they are more soluble and stable than the free bases. All of these compounds have a primary amino group which enables the oxidation product of the developer to couple with the color compounds to form dye images. After removal of the silver image by bleaching and fixing, in a manner well known to the art, the color image remains in the emulsion. A suitable developing solution can be prepared as follows:

Water to make I liter The exposed silver halide emulsions containing the color formers are developed in the above solution in the usual manner. Typical supports for the silver halide emulsion are exemplified by cellulose ester or polyterephthalic acid esters or a nontransparent reflecting medium such as paper or an opaque cellulose ester. The emulsions containing such color formers may be in the form of a single layer on a support or a superimposed layer which may be coated on one or both sides of the support. In the case of a multilayer photographic element, various layers may be differentially sensitized to various regions of the visible spectrum in a known manner.

The present invention has been disclosed with respect to certain preferred embodiments thereof, and there will become obvious to persons skilled in the art various modifications, equivalents or variations thereof which are intended to be included within the spirit and scope of this invention.

What is claimed is:

l. A light-sensitive silver halide photographic emulsion containing a nondifiusing cyan coupler compound of the following formula:

wherein R is selected from the group consisting of hydrogen, and alkyl; R is selected from the group consisting of halogen, hydrogen and SO X wherein X represents hydrogen or a water solubilizing cation; A represents an electron-releasing group selected from the group consisting of alkyl of from six to 18 carbon atoms, OR wherein R represents alkyl of from six to 18 carbon atoms S-R and COOX 1 1 l (a) (fH-COOIIund (b) wnm-oorr-Q Rn l wherein R. represents hydrogen, or carboxyphenylene, n is an integer of l-3 inclusive, and R represents alkyl of one to 18 atoms.

2. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 2-( N- methyl-N-tetradecyl )-amino-5 beta-carboxyethyl l hydroxy-Z-naphthanilide.

3. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 2-(N- methyl-N-tetradecyl )-amino-5 beta-carboxyethyl l hydroxy-2-naphthanilide-4-sulfonic acid.

4. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 2'-( N- methyl-N-tetradecyl )-amino-5 -(,B-bromo-B-carboxyethyl l hydroxy-4-bromo-Z-naphthanilide.

5. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 3-(B- carboxyethyl )-4-[ N methyl-N tetradecyl ]-amino- 1 hydroxy-2-naphthanilide.

6. A light-sensitive silver halide photographic emulsion according to claim I wherein said cyan coupler comprises 2- tetradecyloxy-S ,8-carboxy-B-( p-carboxyphenyl )-ethyl l hydroxy-2-naphthanilide.

7. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 4'- carboxymethoxyl hydroxy-2 'pentadecyl-Z-naphthanilide.

8. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 4-{3- [N-( 3 ,S-dicarboxyphenyl )-N-octadecyl-carbamoyl lpropyloxy} -lhydroxy-2-naphthanilide.

9. A l ig ht-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan couplerconiprises T-[N- (3,S-dicarboxyphenyl)Noctadecylcarbamoyl-methoxy]- l hydroxy-Z-naphthanilide.

10. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 4-[N- (3 ,S-dicarboxyphenyl l hydroxy-Z-naphthanilide.

11. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 1- hydroxy-2-[ 2 -tetradecyloxy-5 -(B-carboxyethyl ]-naphthanilide.

12. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 2- tetradecyloxy-S '-carboxymethoxyl hydroxy-Z-naphthanilide.

13. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 2- pentadecyl-S beta-carboxyethyl 1 hydroxy-2-naphthanilide.

14. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 4'- {3- wherein R is selected from the group consisting of hydrogen, and alkyl; R is selected from the group consisting of halogen, hydrogen and SO X wherein X represents hydrogen or a water solubilizing cation; A represents an electron-releasing group selected from the group consisting of alkyl of from six to [8 carbon atoms OR wherein R represents alkyl of from six to 18 carbon atoms S-R and N wherein R represents lower alkyl of from one to four carbon atoms and R represents alkyl of from eight to 18 carbon atoms; Y is selected from the group consisting of --O and CH and B represents a member selected from the group consisting of 000x (a) (|JH-OOOHand (b) (CHzh-CONQ Re I wherein R6 represents hydrogen, or carboxyphenylene, n is an integer of 1-3 inclusive, and R represents alkyl of H8 atoms.

16. A light-sensitive photographic element comprising a .base coated with the silver halide emulsion of claim l. 

2. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 2''-(N-methyl-N-tetradecyl)-amino-5''-(beta-carboxyethyl)-1-hydroxy-2 -naphthanilide.
 3. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 2''-(N-methyl-N-tetradecyl)-amino-5''-(beta-carboxyethyl)-1-hydroxy-2 -naphthanilide-4-sulfonic acid.
 4. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 2''-(N-methyl-N-tetradecyl)-amino-5''-( Beta -bromo- Beta -carboxyethyl)-1-hydroxy-4-bromo-2-naphthanilide.
 5. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 3''-( Beta -carboxyethyl)-4''-((N-methyl-N-tetradecyl))-amino-1-hydroxy-2-naphthanilide.
 6. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 2''-tetrAdecyloxy-5''-( Beta -carboxy- Beta -(p-carboxyphenyl)-ethyl)-1-hydroxy-2-naphthanilide.
 7. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 4''-carboxymethoxy-1-hydroxy-2''-pentadecyl-2-naphthanilide.
 8. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 4''- 3-(N-(3,5-dicarboxyphenyl)-N-octadecyl-carbamoyl)propyloxy -1-hydroxy-2-naphthanilide.
 9. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 2''-(N-(3,5-dicarboxyphenyl)-N-octadecylcarbamoyl-methoxy)1-hydroxy-2 -naphthanilide.
 10. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 4''-(N-(3,5-dicarboxyphenyl)-N-octadecylcarbamoylmethoxy)-1-hydroxy-2 -naphthanilide.
 11. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 1-hydroxy-2-(2''-tetradecyloxy-5''-( Beta -carboxyethyl))-naphthanilide.
 12. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 2''-tetradecyloxy-5''-carboxymethoxy-1-hydroxy-2-naphthanilide.
 13. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 2''-pentadecyl-5''-(beta-carboxyethyl)-1-hydroxy-2-naphthanilide.
 14. A light-sensitive silver halide photographic emulsion according to claim 1 wherein said cyan coupler comprises 4''- 3-(N-3,5-(dicarboxyphenyl)-N-octadecyl-carbamoyl)propyloxy -2''-(N-tetradecyl-N-methyl)amino-1-hydroxy-2-naphthanilide.
 15. A process of producing a cyan dyestuff image in a silver halide emulsion which comprises exposing said emulsion to light and developing the same with the primary aromatic amino developer in the presence of a cyan color former having the following formula:
 16. A light-sensitive photographic element comprising a base coated with the silver halide emulsion of claim
 1. 